Ternary catalyst systems for the polymerization of cyclic olefins

ABSTRACT

A METHOD FOR THE RING OPENING POLYMERIZATION OF UNSATURATED ALICYCLIC COMPOUNDS CONTAINING AT LEAST FOUR AND NOT MORE THAN FIVE CARBON ATOMS IN THE CYCLIC RING AND UNSATURATED ALICYCLIC COMPOUNDS CONTAINING AT LEAST EIGHT CARBON ATOMS AND AT LEAST ONE DOUBLE BOND IN THE CYCLIC RING IS DISCLOSED, WHICH COMPRISES SUBJECTING SUCH UNSATURATD ALICYCLIC COMPOUNDS TO A CATALYST SYSTEM COMPRISING (A) AT LEAST ONE TRANSITION METAL SALT FROM THE GROUP OF TUNGSTEN HALIDES, TUNGSTEN OXYHALIDES, MOLYBDENUM HALIDES AND MOLYBDENUM OXYHALIDES, (B) AT LEAST ONE ORGANOMETALLIC COMPOUND WHEREIN THE METAL IS SELECTED FROM THE GROUPS IA IIA, IIB, IVA AND VA OF THE PERIODIC SYSTEM AND (C) AT LEAST ONE LEWIS ACID OF THE FORMULA M-XN WHERE MA IS A METAL FROM THE GROUP OF ALUMINUM, ZINC, GALLIUM,TIN AND ANTIMONY; X IS A HALOGEN AND N EQUALS THE VALENCE OF M.

United States Patent U.S. Cl. 260-882 R 15 Claims ABSTRACT OF THE DISCLOSURE A method for the ring opening polymerization of unsaturated alicyclic compounds containing at least four and not more than five carbon atoms in the cyclic ring and unsaturated alicyclic compounds containing at least eight carbon atoms and at least one double bond in the cyclic ring is disclosed, which comprises subjecting such unsaturated alicyclic compounds to a catalyst system comprising (A) at least one transition metal salt from the group of tungsten halides, tungsten oxyhalides, molybdenum halides and molybdenum oxyhalides, (B) at least one organometallic compound wherein the metal is selected from groups Ia, Ila, IIb, lVa and Va of the Periodic System and (C) at least one Lewis acid of the formula MX where M is a metal from the group of aluminum, zinc, gallium, tin and antimony; X is a halogen and n equals the valence of M.

This application is a continuation of Ser. No. 755,375 filed Aug. 26, 1968, now abandoned.

This invention relates to a process for polymerizing unsaturated alicyclic compounds and to the products resulting therefrom. In its broad aspect, the invention is directed to the preparation of polymers derived from unsaturated alicyclic compounds which contain at least one alicyclic ring structure containing at least two carbon atoms connected through a double bond.

The polymerization process of this invention may be used to prepare novel solid polymers. The properties and characteristics can be tailor made to fit a wide variety of uses and fields of application. The properties of the polymers resulting from the polymerization process of this invention can be varied over a wide range depending on (1) the particular unsaturated alicyclic monomer chosen to be polymerized, (2) the particular polymerization catalyst employed and (3) the particular polymerization conditions employed. The products resulting from the O polymerization of this invention can be employed in a variety of applications; for example, they ma be employed to produce finished rubber articles such as pneumatic tires, molded goods and the like or they may be materials which are useful to manufacture articles such as films and fibers. They may also be employed to form finished products by molding techniques.

This invention comprises polymerizing at least one alicyclic compound selected from the group consisting of (l) unsaturated alicyclic compounds containing at least four and not more than five carbon atoms in the cyclic ring and containing one carbon-to-carbon double bond in the cyclic ring, and (2) unsaturated alicyclic compounds containing at least eight carbon atoms in the cyclic ring and containing at least one carbon -to-carbon double bond in the cyclic ring, by subjecting said alicyclic compounds to ring opening polymerization conditions, in the presence of a catalyst comprising (A) at least one transition metal salt selected from a group consisting of tungsten halides, tungsten oxyhalides, molybdenum halides and molybdenum oxyhalides, (B) an organometallic compound selected from a group consisting of Ia, IIa, IIb, Wu and Va of the Periodic Table of Elements and (C) at least one Lewis acid of the formula MX where M is a metal selected from a group consisting of aluminum, zinc, gallium, tin and antimony; X is a halogen selected from a group consisting of chlorine, bromine, iodine and fluorine and n is an integer equal to the valence of M.

The Periodic Table of Elements referred to above may be found in the Handbook of Chemistry and Physics, 44th Edition, April 1962 reprinted, page 448, published by the Chemical Publishing Company, Cleveland, Ohio, USA.

Representative examples of the tungsten and molybdenum halides useful as the first or (A) catalyst component of this invention include molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexafluoride, tungsten dibromide, tungsten pentabromide, tungsten hexabromide, tungsten dichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, tungsten hexafluoiide, tungsten diiodide and tungsten tetraiodide.

Representative examples of the tungsten and molybdenum oxyhalides useful as the first or (A) catalyst component of this invention include molybdenum oxytetrachloride, molybdenum oxytetrafluoride, tungsten oxytetrabromide, tungsten, oxytetrachloride and tungsten oxytetrafluoride. The preferred metal halides and metal oxyhalides are those of tungsten. The most preferred include tungsten hexachloride, tungsten hexafluoride, tungsten oxytetrachloride and tungsten oxytetrafluoride.

Representative examples of metals from which the organometallic compound, the second or (B) catalyst component of this invention, can be derived are lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, Zinc, cadmium, mercury, silicone, germanium, tin, lead, arsenic antimony and bismuth. The preferred organometallic compounds are compounds of lithium, sodium, magnesium, tin and zinc.

Representative examples of organometallic compounds useful as the second or (B) catalyst component of this invention are compounds having as the metal component lithium, magnesium, tin and zinc. Representative examples of such compounds include alkyllithiums such as methyllithium, ethyllithium, butyllithium and the like; aryllithiums such as phenyllithium, p-chlorophenyllithium and the like; alkyl tin compounds such as diethyldimethyltin, tetraethyltin, tetraisoamyltin, tetramethyltin and the like; aryltins such as tetraphenyltin, tetra-o-tolyltin, tetra-p-tolyltin and the like; alkylzinc compounds such as dimethylzinc, diethylzinc, diisopropylzinc and the like; and Grignards such as phenylmagnesium bromide and the like. It is usually preferred to employ such compounds as alkyllithium, alkyltin and alkylzinc.

Representative examples of the metals from which the Lewis acid, the third or (C) catalyst component of this invention, can be derived include aluminum, zinc, gallium, tin and antimony. The most preferred metal is that of aluminum.

Representative examples of the Lewis acid, the third or (C) catalyst component employed in this invention include aluminum trihalides such as aluminum trichloride, aluminum tribromide and the like; zinc dihalides such as zinc dichloride, zinc dibromide and the like; gallium trihalides such as gallium tribromide, gallium trichloride, gallium trifluoride and the like; tin tetrahalides such as tin tetrachloride, tin tetrabromide and the like; and antimony pentahalides such as antimony pentachloride, antimony pentabromide and the like. The most preferred Lewis acid compounds are those of aluminum trihalides.

The catalysts employed in this invention are prepared by mixing the components by known techniques. Thus, the catalysts may be prepared by preformed or in situ techniques. By preformed is meant the manner in which the catalyst components are mixed together prior to exposure of any of the catalysts components to the monomer to be polymerized. By in situ is meant that the catalyst components are added separately to the monomer to be polymerized. The catalyst components can be mixed either as pure compounds or as suspensions or solutions in liquids which do not adversely effect the ring opening polymerization.

While the presence of the monomer is not essential during the formation of an active catalyst species by mixing of (A), (B) and (C) and this fact facilitates the use of preformed" catalysts, it has been found that freshly preformed catalysts are generally more active than catalysts which have been allowed to age before use.

The amount of catalyst employed may be varied over a wide range of concentrations. Any establishment of an arbitrary catalytic concentration for one of the catalyst components will determine the relative concentrations of the remaining two catalyst components. Thus, the relative concentrations of the catalyst components, (A), (B) and (C), are interdependent. This interdependency of the catalyst components (A), (B) and (C) also depends on a number of other factors such as temperature, reactant used, purity of reactant, reaction times desired and the like. Of course, a catalytic amount, about x10 moles, of catalyst must be employed and those skilled in the art will be readily able to determine the optimum catalytic range.

It has been found that successful results are obtained in the practice of this invention when the molar relationship between the catalyst components (A), (B) and (C) as previously defined, are within a molar ratio of A/B ranging from 0.2/1.0 to about 2.0/1.0, a molar ratio of A/C ranging from 0.1/1.0 to about 1.0/1.0, and a molar ratio of B/C ranging from 0.09/ to about 4.0/1.0.

Various unsaturated alicyclic compounds may be employed in the practice of this invention. As is mentioned above, unsaturated alicyclic compounds containing at least 4 and not more than 5 carbon atoms in the cyclic ring which contain one carbon-to-carbon double bond in the cyclic ring and unsaturated alicyclic compounds containing at least 8 carbon atoms in the cyclic ring which contain at least one carbon-to-carbon double bond in the cyclic ring are operable in this invention.

The preferred unsaturated alicyclic compounds of this invention are those comprising a single unsaturated alicyclic ring. These alicyclic rings may be monoor multi-substituted by such groups as alkyl, aryl, arylalkyl, and halogen groups.

Representative examples of unsaturated alicyclic compounds containing a single alicyclic ring having at least 4 and not more than 5 carbon atoms in the cyclic ring and containing one double bond in said ring are cyclobutene and cyclopentene. Representative examples of compounds having at least 8 carbon atoms in the cyclic ring and having from one to two double bonds in said ring are cyclooctene; 1,4- and 1,5-cyclooctadiene. Representative of compounds having nine carbon atoms and one to three double bonds in the ring are cyclononene, 1,4- and 1,5-cyclononadiene and 1,4,7-cyclononatriene. Representative of compounds having 10 carbon atoms and one to three double bonds in the ring are cyclodecene, 1.4-, 1,5- and 1,6-cyclodecadiene and 1,4,6- and 1,4,7- cyclodecatriene. Representative of compounds having 11 carbon atoms and one to three double bonds in the ring are cycloundecene, 1,4-, 1,5- and 1,6-cycloundecadienes and 1,4,7- and 1,4,8-cycloundecatriene. Representative of compounds having 12 carbon atoms and one to three double bonds in the ring are cyclododecene, 1,4-, 1,5-, 1,6- and 1,7-cyclododecadiene and 1,4,7-, 1,4,8-, 1,4,9- and 1,5,9-cyclododecatriene.

The most preferred unsaturated alicyclic compounds of this invention are those containing from one to three carbon-to-carbon double bonds in the ring and in which the double bonds are located in relation to each other in a manner that they are not adjacent and are nonconjugated. Representative examples of such preferred materials are cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene and 1,5,9-cyclododecatriene.

Still another class of preferred unsaturated alicyclic monomers are those containing one carbon-to-carbon double bond in the ring of at least 4 and not more than 5 carbon atoms, examples of which are cyclobutenc and cyclopentene. Another group which are preferred are those which have at least 8 carbon atoms in the ring and not more than 12 carbon atoms in the ring and contain 1, 2, or 3 carbon-to-carbon double bonds in said ring, examples of which are previously set forth.

Representative examples of substituted unsaturated alicyclic compounds are alkyl-substituted compounds such as 1,5,9-trimethylcyclododecatriene; aryl-substituted compounds such as 3-phenylcyclooctene-1; aralkyl-substituted compounds such as 3-benzylcyclooctene-1; alkaryl-substituted compounds such as 3-methylphenylcyclooctene-1; halogen-substituted compounds wherein the halogens are iodine, chlorine, bromine and fluorine such as 5-chlorocyclooctene-l, 3-bromocyclooctene-1, 5 -chlorocyclododecene1, and 5,6-dichlorocyclooctene-1. Mixtures of the unsaturated alicyclic compounds may be polymerized including both substituted unsaturated alicyclic compounds and the unsubstituted unsaturated alicyclic compounds.

The polymerizations of this invention may be conducted in solution or in bulk. When the polymerization is carried out in solution, solvents which do not adversely affect the polymerization are desired. Representative of useful solvents are liquid aromatic hydrocarbons such as benzene and toluene; hydrogenated aromatic hydrocarbons such as Tetralin; liquid aliphatic hydrocarbons such as pentane, heptane, hexane, petroleum ether, decane; and alicyclic hydrocarbons such as cyclohexane, Decalin and cyclooctane. Mixtures of such solvents may also be used.

Temperatures at which the polymerization reaction is carried out can be varied over a wide range. Usually the temperature can be varied from extremely low temperatures such as 60 C. up to high temperatures such as 150 C. or higher. Thus, the temperature is not a critical factor of the invention. It is generally preferred, however, to conduct the reaction at a temperature in the range of from about -20 C. to about C. The pressure at which the polymerization is carried out can also be varied over a wide range. The reaction can be conducted at atmospheric pressure or, if desired, it can be carried out at sub-atmospheric pressure or super-atmospheric pressure. Generally, a satisfactory polymerization is obtained when the reaction is carried out at about autogenous pressure, developed by the reactants under the operating conditions used.

The polymerization time will vary and can range from a few seconds to 24 hours or more, depending upon the polymerization conditions and the degree and extent of polymerization desired.

The polymerization reaction may be carried out as a batch or as a continuous process. In preforming the polymerizations of this invention, the introduction of the monomer, catalyst, and solvent, when a solvent is employed, can each be made to the reaction Zone alternately, intermittently, and/ or continuously.

It is thought that the polymerizations of this invention take place through a ring-opening polymerization mechanism. Such ring-opening polymerizations of unsaturated alicyclic compounds can be used to make a number of alternating copolymers and terpolymers that have not been capable of being made before. For example, the ringopening polymerization of cyclooctene yields a polyoctenamer which may be considered the alternating copolymer of one butadiene unit and two ethylene units.

The ring opening polymerization of cyclooctadiene-l,5 leads to a polybutenamer which is equivalent to the 1,4-

In these applications the monomer may be polymerized in the presence of one or more rein-forcing carbon blacks, pigments or resins an certain antioxidants. The products made by this procedure may be crosslinked :by adding addition polymer of butadiene-LS. In practicing this inpolymerizable polyfunctional compounds, for example yention, polybutenamers can be formed whose structure bicyclopentadiene, to the main monomer. The molded comprises alternating cisand trans-vinylene groups in products made by ring-opening polymerization may be successive polymeric repeat units which is equivalent to crosslinked by exposure to ionizing radiation such as the polymer which may be obtained by the 1,4-addition gamma rays, X-rays, or electrons. These molded prodpolymerization of butadienc-L3 in Which cessive bu ucts may also be crosslinked or vulcanized by incorporatdiene-1,3 units alternately occur in cisand trans-configin certain compounds which on heating during or suburations. Such a polymer could be considered an alternatsequent t th polymerization ill l d t ti l 8 copolymer of and trans-1,4 P y( crosslinking or vulcanization of these polymers.

The ring opening Polymerization of 5-methylcyclooc- The polymerization reaction may be terminated by fem-1 would Yield the alternating tefpolymef 0f butaincorporating various compounds which, upon heating, dime-1,3, P py and ethylene; likewise, -p y release materials which deactivate the catalyst. Repre- CIOOC e e-I Would 346111 the alternating terpolymef of sentative examples of such compounds are the ammonia i Styrene and ethylene- The Tiflg Opening P salts such as ammonium chloride, ammonium carbonate, lymerization of S-methylcyclooctadiene-l,5 would yield ammonium acetate, ammonium oleate ammonium the alternating copolymer of butadiehe-lfi and isoplenephate, and ammonium phosphate; other ammonia-releas- The g Opening Polymerization of Substituted Y ing compounds such as tetraalkyl ammonium halides, e.g., decc es c yield even more complicatfid alternatmg tetramethyl ammonium chloride, water-releasing agents P y terpolymefs, and quadnpolymerssuch as salts with water of crystallization, examples of Ring opening polymerization also allows one to make which are: A12(SO4).17H2O; NHiAKSO 4) copolymers and terpolymcrs that have not heretofore been made by ordinary addition polymerizations. A representai' 2 tive example of such a polymerization is the ring-open- M I-IPO -7H O; KA1(SQ4)2-12H2'(); K -5 ing polymerization of cyclononene which yields the per- N B O -10H 0; Na CO -10H O; NaHPOy IZH- O; fectly alternating copolymer of butadiene-L3 and P N so. 0 methylene. a2 4 2 Ring opening polymerization of halogen-substituted unand ZnNO 6H O. saturated alicyclic monomers also leads to interesting co- The following examples are set forth t f th m polymers and terpolymcrs; for ins ance, y trate the nature of this invention. However, it should tene-l would lead to a polymer equivalent to an alternatbe understood that the examples are set forth for illusing ihterpolymer Of hUtadieHe-m P1118 Vinyl Chloride and trative and not for limitative purposes. All experiments ethylene; 3-bfomocyclooctene'l would yield P y Were conducted in an atmosphere of nitrogen unless equivalent 110 all alternating interpolymel 0f ethylen6 P noted. Column 1 sets forth the experimental number. 1-bromobutadiene-1,3 and ethylene and S-chlorocyclodocolumns 2, 3 and 4 Set f th the number f moles f decen-l Wo lead to a IJOIYIIIer equivalent to an alter AlCl WC1 and organometallic respectively. Column nating interpolymer of butadiene-l,3 plus vinyl chloride 5 sets f th the Order f i i f the catalyst and 3 ethylene molecules. ponents and column 6 gives the weight percent yield of Ring opening polymerization of unsaturated alicyclic Polymer u i hydrocarbons containing at least 4 and not mgre than EXAMPLE I 5 carbon atoms and containing one carbon-to-car on double bond in the cyclic ring and those containing 8 carbon A senes of earned out atoms and at least one carbon-to-carbon double bond in (gms') of y (mulled .cyclooctene 80 the cyclic ring produces high molecular weight polymers tel-S y dned F In each Polymenza' tron. All manipulations of charging monomer, solvent and which have a high degree of resistance to oxidation.

. catalyst components were conducted under a nitrogen Bulk polymerizations may be desirable from a process atmos here A 0 02 01 (M 1 f t t standpoint as relatively little heat appears to be evolved p l {n ar so u Ion o u-ngs en d hexachloride (WCI in benzene, a 0110 M solution of P 11101? unatflrate l allcydfc 9 P1Ymeme butyllithium (BuLi) and a 0.15 M slurry of finely divided in practicing this invention. This constitutes a great adaluminum chloride (A103) in benzene, were prepared vantage for this ring opening type of polymerization over and employed in the amounts presented in the following COIlVfiIlfiOIlal addition polymefilatlontable. Termination was accomplished by injecting 5 The low Volume decreases accompanying a gp ml. of a 10 percent by weight solution of ditertiary-butyling polymerization is another major advantage over conp-cresol in a 50/50 mixt r of th l d .b

Organo- AlCla WGla metallic moles moles moles Order of Yield, X104 X104 X104 addition percent Experiment N 0.:

1 3 1 0.9 45.9 i i; i a: 4.5 i 0.0 100.0

EXAMPLE II ventional addition polymerization, particularly where these monomers are bulk polymerized to form potting compounds and various articles, examples of which are molded plastic materials, molded rubber-like goods, shoe soles and heels, industrial belts and vehicle tires.

AlCla plus WOla Organo- .AlCla mixture metallic moles moles moles Order 01 Yield, X10 X10 X10 addition percent Experiment N 0.:

1 1 1. 2 Li (\V-Al) 19. 1 1 1 2. 1 47. 8 1. 1 1. 8 52. 3 2 1 1. 5 51. 4 3 1 1. 2 Z 5 l 2. 1 a 1 0. 0 A1 95. 1 9 1 l. 2 $18. 0 t) 1 1. 5 00. 4 1) 1 2. 1 100. 0 9 1 3. 0 05. 8

EXAMPLE III A series of polymerizations was carried out similar to Example I except that two additional organometallic compounds were employed. They were 0.10 molar (M) U1 and a molar ratio of B/C ranging from about 0.09/ 1.0 to about 4.0/1.0.

3. A process according to claim 1 in which the transition metal salt is selected from the group consisting of tungsten hexachloride, tungsten hexafiuoride, molybdenum pentachloride and molybdenum hexafiuoride.

4. A process according to claim 1 in which the transition metal salt is selected from the group consisting of tungsten oxytetrachloride, tungsten oxytetrafluoride, molybdenum oxytetrachloride and molybdenum oxytetrafluoride.

5. A process according to claim 1 in which the organometallic compound is selected from the group consisting of organolithium, organotin and organozinc compounds.

6. A process according to claim 1 in which the Lewis acid is an aluminum halide compound.

In another experiment, wherein a preformed catalyst consisting of AlCl and WCl with a mole ratio of Al/W of about 1.0, tetrabutyl tin (1.25 X 10* moles) was added to 1.0 10- moles of the preformed AlCl /WCl to give a polymer yield of 47.7%.

While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

What is claimed is:

1. A ring-opening polymerization process comprising polymerizing at least one unsaturated alicyclic compound selected from the group consisting of (1) unsaturated alicyclic compounds containing at least four and not more than five carbon atoms in the cyclic ring and containing one carbon-to-carbon double bond in the cyclic ring, and (2) unsaturated alicyclic compounds containing at least eight carbon atoms in the cyclic ring and containing at least one carbon-to-carbon double bond in the cyclic ring, by subjecting said alicyclic compounds to polymerization conditions in the presence of a catalyst system comprising (A) at least one transition metal salt selected from a group consisting of tungsten halides, tungsten oxyhalides, molybdenum halides and molybdenum oxyhalides, (B) at least one organometallic compound wherein the metal is selected from the group consisting of Ia, Ila, IIb, IVa and Va of the Periodic Table of Elements and (C) at least one Lewis acid of the formula MX where M is a metal selected from the group consisting of aluminum, zinc, gallium, tin and antimony; X is a halogen selected from the group of bromine, chlorine, iodine and fluorine; and n is an integer equal to the valence of M.

2. A process according to claim 1 in which the molar relationship between the catalyst components defined by (A), (B) and (C) are within the molar ratio of A/B ranging from about 0.2/1.0 to about 2.0/1.0; a molar relationship of A/ C ranging from about 0.01/ 1.0 to about 7. A process according to claim 1 in which the unsaturated alicyclic compound contains at least four and not more than five carbon atoms and only one carbon-tocarbon double bond in the cyclic ring.

8. A process according to claim 1 in which the unsaturated alicyclic compound contains at least eight and not more than twelve carbon atoms in the cyclic ring and contains from one to three carbon-to-carbon double bonds in the cyclic ring which are located in a relation to each that they are not conjugated.

9. A process according to claim 1 in which cyclooctene is homopolymerized.

10. A process according to claim 1 in which cyclooctadiene is homopolymerized.

11. A process according to claim 1 in which cyclododecatricne is homopolymerized.

12. A process according to claim 1 in which cyclooctadiene and cyclododecatriene are copolymerized.

13. A process according to claim 1 in which polymerization is conducted in bulk.

14. A process according to claim 1 in which polymerization is conducted in solution.

15. A process according to claim 1 wherein the catalyst components (A), (B) and (C) can be employed in situ or preformed before exposure to monomer.

References Cited UNITED STATES PATENTS 3,074,918 l/1963 Eleuterio 260-93.l 3,449,310 6/1969 Dall Asta 26093.1 3,458,489 7/1969 Natta et a1. 26093.1 3,459,725 8/1969 Natta et al. 260-93.1 3,476,728 11/1969 Natta et al. 260-93.1

JOSEPH L. SCHOFER, Primary Examiner R. A. GAITHER, Assistant Examiner US. Cl. X.R. 260--93.1 

